Lead-free optical glasses

ABSTRACT

The invention can relate to essentially lead-free optical glasses having a refractive index nd of from about 1.65 to about 1.87 and an Abbe number νd of from about 27 to about 43 and a composition (in % by weight, based on oxide) of SiO2 about 10-about 25, B2O3&gt;about 10-about 25, Na2O about 2.5-about 10, K2O 0-about 3, CaO about 0.5-about 5, BaO about 15-about 30, ZnO about 5-about 15, TiO2 about 6-about 15, ZrO2 about 0.5-about 8, Y2O3 about 0.1-about 2, La2O3 about 0.5-about 8, Nb2O5 about 6-about 12, with La2O3+Nb2O5&lt;=about 17,Ta2O5 0-about 1, and Gd2O3 0-about 1.

FIELD OF THE INVENTION

The present invention relates to essentially lead-free optical glasses, and more particularly to essentially lead-free optical glasses having refractive indexes n_(d) of from about 1.65 to about 1.87 and Abbe numbers ν_(d) of from about 27 to about 43.

BACKGROUND OF THE INVENTION

Because the glass components PbO and As₂O₃ have entered public debate as environmental pollutants, there is a demand by the manufacturers of optical equipment for 10 PbO-free and preferably also As₂O₃-free glasses having the optical properties substantially the same as glasses having these oxides.

Simple replacement of lead oxide by one or more constituents generally does not succeed in reproducing the desired optical and glass-engineering properties affected by PbO. Instead, new developments or extensive changes in the glass composition are necessary.

The patent literature reveals some specifications which have already described lead-free glasses having optical values from the stated range and having similar compositions. However, the glasses have a wide variety of disadvantages.

Both the glasses of the unexamined Japanese publication JP 62-100 449 A, having refractive indexes n_(d) of from 1.64 to 1.88, and those of JP 60-22 133 8 A, having refractive indexes n_(d) of from 1.62 to 1.85, contain Li₂O as a required constituent, contents of up to 15 and 12% by weight respectively being possible. Li₂O-containing glasses of this type are very susceptible to crystallization. The same also applies to the glasses of JP 63-170 247 A, which contain at least 5 mol-% of Li₂O.

The glasses of the first-mentioned specification also contain from 2 to 20% by weight of Sb₂O₃. Use of this component in such amounts makes increased safety precautions necessary during production.

DE-A 35 34 575 Al relates to glasses having refractive indexes n_(d)≦1.59 for eyeglass lenses having color contrast amplification. The glasses, which vary greatly in their composition, contain various coloring components in a base glass containing up to 33% by weight of Nd₂O₃.

The glasses of JP 53-90 312 A have relatively low refractive indexes of n_(d)≦1.67. They contain at least 3% by weight of the glass former Al₂O₃ in order to counter the tendency toward crystallization caused by the relatively high content of alkaline earth metal oxides, but this has a disadvantageous effect on the melting properties and the “length” of the glass. The latter also applies to the Al₂O₃- and F-containing glasses of JP 1-133956 A having low refractive indexes. The glasses of JP 62-126 33 A, which likewise have low refractive indexes, contain expensive Cs₂O as a required component and have high proportions of SiO₂ of from 30 to 75 mol-%.

German Patent Specification DE 32 01 344 C2 describes high-refractive index glasses having a refractive index n_(d)≦1.79 in which BaO is only an optional component and which contain high proportions of at least 13% by weight of the expensive component La2O₃, which promotes crystallization at these rather high contents.

JP 52-25812 A and JP 58-46459 B2 describe flint glasses from the SiO₂—Nb₂O₅—TiO₂—R₂O(—RO) system, where some of the Nb₂O₅ can be replaced by Ta₂O₅ and some of the SiO₂ can be replaced by B₂O₃. The B₂O₃ content should not exceed 10% by weight and 5% by weight respectively (based on all the glass) owing to crystallization phenomena.

SUMMARY OF THE INVENTION

As used herein, the term “essentially component-free” means a material having an extremely low level of the referenced component, such as, for example, an unavoidable impurity.

A feature of the invention is to provide lead-free, an essentially desirably lead-free, optical glass having a refractive index n_(d) of from about 1.65 to about 1.87 and an Abbe number ν_(d) of from about 27 to about 43 which have good melting and processing properties and are inexpensive to produce.

This feature can be achieved by the glasses described as lead-free optical glasses having a refractive index n_(d) of from 1.65 to 1.87 and an Abbe number ν_(d) of from 27 to 43, and including the following composition (in % by weight, based on oxide): SiO₂ 10-25, B₂O₃>10-25, Na₂O 2.5-10, K₂O 0-3, CaO 0.5-5, BaO 15-30, ZnO 5-15, TiO₂ 6-15, ZrO₂ 0.5-8, Y₂O₃ 0.1-2, La₂O₃ 0.5-8, Nb₂O₅ 6-12, with La₂O₃+Nb₂O₅≦17, Ta₂O₅ 0-1, Gd₂O₃ 0-1and optionally a fining agent.

The glasses can include the glass formers SiO₂ (about 10-about 25% by weight) and B₂O₃ (>about 10-about 25% by weight) in balanced proportions. This produces both good melting properties of the glasses, which generally improve with increasing B₂O₃ content and generally worsen with increasing SiO₂ content, and good chemical resistance, which would generally worsen at an excessive B₂O₃ content. The B₂O₃ content also can contribute to the good devitrification stability. It has been found that the devitrification tendency would generally increase excessively if said minimum B₂O₃ content were reduced. The B₂O₃ content is preferably at most about 20% by weight. Particular preference is given to a B₂O₃ content of from about 14 to about 19% by weight. The SiO₂ content is preferably at least about 15% by weight and particularly preferably at most about 20% by weight.

Desirably, the glasses include about 15-about 30% by weight of BaO. This proportion of BaO is required in order to achieve the desired Abbe number region. The BaO content is preferably at least about 18% by weight. Particular preference is given to a content of at least about 25% by weight. Especially due to the balanced proportions of B₂O₃ and SiO₂ in relation to the BaO content, the melting properties of the glasses can be particularly good. In addition to BaO, the glasses can include about 0.5-about 5% by weight, preferably about 0.5-about 3% by weight, particularly preferably about 0.5-about 2.5% by weight, of CaO. The presence of CaO in addition to BaO can improve the crystallization stability of the glasses, as does the presence of ZnO, of which the glass can include about 5-about 15% by weight, preferably about 5-about 12% by weight, for stabilization and in order to set the high refractive index. Particular preference is given to a ZnO content of from about 7 to about 11% by weight.

The glasses can include both TiO₂ (about 6-about 15% by weight, particularly preferably about 7-about 12% by weight) and ZrO₂ (about 0.5-about 8% by weight, preferably about 1-about 5% by weight, particularly preferably at least about 2.5% by weight). These two components can improve the chemical resistance, in particular the alkali resistance. At higher contents, the crystallization stability could be greatly reduced.

It is particularly preferred for the glasses to include ZrO₂ and TiO₂ in a certain ratio, more precisely in a ZrO₂/TiO₂ weight ratio of from about 0.06 to about 0.85. This ratio can make it easier to achieve a high refractive index at the same time as a low Abbe number. Desirably, it is satisfied with ZrO₂ in an amount of from about 1 to about 5% by weight.

Desirably, the glasses include about 0.5-about 8% by weight, particularly preferably about 0.5-about 2% by weight, of La₂O₃ and about 6-about 12% by weight, preferably about 6-about 10% by weight, particularly preferably about 7-about 9.5% by weight, of Nb₂O₅. These ranges facilitate the desired optical position, in particular low Abbe numbers at the same time as high refractive indexes. In addition, both components can increase the transmission of the glasses. A further increase in the content could result in deviating n_(d) and ν_(d) values and an unnecessary increase in the cost of the batch. A sum (La₂O₃+Nb₂O₅)≦about 17% by weight, preferably≦about 14% by weight, should therefore not be exceeded, particular preference being given to (La₂O₃+Nb₂O₅)≦about 11% by weight.

In order to vary and precisely set the low Abbe number at the same time as a high refractive index, desirably the glasses include about 0.1-about 2% by weight of Y₂O₃ and can also contain up to about 1% by weight of each of Gd₂O₃ and Ta₂O₅. However, it is preferred to omit Gd₂O₃ and Ta₂O₅. The Y₂O₃ content is preferably at least about 0.2% by weight, with a Y₂O₃ content of at most about 0.5% by weight being particularly preferred.

In order to improve the melting properties, the glasses contain from about 2.5 to about 10% by weight of Na₂O and can include up to about 3% by weight of K₂O. At higher contents of each, crystallization could be increased. The component Li₂O, which likewise promotes crystallization, is usually not required. The glasses preferably can include at most about 8% by weight of Na₂O and contain no K₂O. Even more preference is given to a content of at most about 7% by weight of Na₂O, with an Na₂O content of from about 3 to about 6% by weight being particularly preferred.

Depending on the restrictions on the respective ranges of the components, the ranges of the glasses' optical data can also be restricted.

Thus, glasses having a refractive index n_(d) of from 1.66 to 1.85 and an Abbe number ν_(d) of from 28 to 42 can be obtained in the following composition range (in % by weight, based on oxide) : SiO₂ 10-25, B₂O₃ 10-20, Na₂O 2.5-8, CaO 0.5-3, BaO 18-30, ZnO 5-12, TiO₂ 6-15, ZrO₂ 1-5, Y₂O₃ 0.2-2, La₂O₃ 0.5-8, Nb₂O₅ 6-14, La₂O₃+Nb₂O₅≦14, Ta₂O₅ 0-1, Gd₂O₃ 0-1.

Glasses having refractive indexes n_(d) of from 1.70 to 1.79 and Abbe numbers ν_(d) of from 30 to 39 can be found in the following composition range (in % by weight, based on oxide): SiO₂ 15-25, B₂O₃ 10-20, Na₂O 2.5-7, CaO 0.5-3, BaO 18-30, ZnO 5-12, TiO₂ 6-15, ZrO₂ 1-5, Y₂O₃ 0.2-2, La₂O₃ 0.5-8, Nb₂O₅ 6-14, La₂O₃+Nb₂O₅≦14 .

Glasses from the composition range (in % by weight, based on oxide): SiO₂ 15-20, B₂O₃ 14-19, Na₂O 3-6, CaO 0.5-2.5, BaO 25-30, ZnO 7-11, TiO₂ 7-12, ZrO₂ 2.5-5, Y₂O₃ 0.2-0.5, La₂O₃ 0.5-2, Nb₂O₅ 7-9.5, La₂O₃+Nb₂O₅≦11, can have refractive indexes n_(d) of from 1.73 to 1.77 and Abbe numbers ν_(d) of from 33 to 37.

Generally, in order to improve the glass quality, one or more fining agents such as conventional fining agents, can be added to the batch in the usual amounts in order to fine the glass. Desirably, the glass thus has particularly good internal glass quality with respect to freedom from bubbles and streaks. As an example, As₂O₃ can be used in an amount of up to and including 1% by weight.

If the fining agent used is not As₂O₃, but instead, for example, Sb₂O₃, which is generally possible without losses with respect to the glass quality, the essentially lead-free glasses according to the invention can be in addition essentially free from arsenic.

The Sb₂O₃ content is preferably from about 0.1 to about 0.5% by weight. It is furthermore preferred for the glasses, where appropriate also in addition to Sb₂O₃, to include up to about 0.5% by weight of fluoride, which likewise has a fining action. Fluoride can be added, for example, as CaF₂ or even NaF.

The glasses according to the invention have the following advantages in addition to the desired optical properties:

The glasses can be essentially or preferably PbO-free, and, in a preferred embodiment, also essentially As₂O₃-free or desirably As₂O₅-free. The glasses can have good crystallization stability, evident from a low upper devitrification limit. This can enable production in a continuous melting unit. A measure of a crystallization stability which can be adequate for production of this type is the viscosity at the upper devitrification limit. For continuous production, it should be≧about 1000 dPas. This can be satisfied by the glasses according to the invention. Such a crystallization stability of the glasses may also enable further thermal treatment of the glasses, such as pressing or re-pressing.

The glasses may not only have good processing properties, but can also have good melting properties. Generally, this is also evident from their melting points of about 1200° C.

The glasses can have excellent alkali resistance, generally evident from their classification in alkali resistance glass AR=1, while also otherwise having adequate chemical resistance. The chemical resistance of the glasses can be of importance for their further treatment, such as grinding and polishing.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.

In the foregoing and in the following examples, all temperatures are set forth uncorrected in degrees Celsius; and, unless otherwise indicated, all parts and percentages are by weight.

The entire disclosure[s] of all applications, patents and publications, cited above [or below], and of corresponding German application No. 19920865.4-45, filed May 6, 1999 is hereby incorporated by reference.

EXAMPLE

Seven (7) examples of glasses according to the invention were produced from conventional raw materials.

Table 2 shows the respective compositions (in % by weight, based on oxide), the refractive index n_(d), the Abbe number ν_(d), the partial dispersion in the blue region of the spectrum P_(g,F), and the anomaly of this partial dispersion ΔP_(g,F)[10⁻⁴], the density ρ[g/cm³], the coefficient of thermal expansion α_(20/300)[10⁻⁶/K], the glass transition temperature T_(g)[° C.] of the glasses, and for some of the examples also the upper devitrification limit UDL [° C.].

If the relative partial dispersion Px, y for the wavelengths x and y can be defined by the equation

Px,y=(nx−ny) / (nF−nC)  (1)

then as Abbe showed the following linear relationship will probably apply, to so called “normal glasses”:

Px,y=axy+b xy·nd=Px,y  (2)

Correction of the secondary spectrum, i.e., achromatization for more than two wavelengths, sometimes necessitates the use of at least one glass type which does not conform with this rule.

Therefore it is desirable to find a glass that deviates noticeably from Abbe's empirical rule; that is, glasses which possess deviating partial dispersions.

A measure of this deviation is the ordinate difference DP given by the respective P-nd-point displaced from Abbe's “normal line”. Instead of equation (2) the following generally valid relationship is used.

Px,y=a xy+b xy·nd+DPx,y=Px,y+DPx,y  (3)

The term DPx,y is thus a quantitative description of dispersion behavior that differs from that of “normal glasses”.

The deviations Dp from the “normal lines” for the following five relative partial dispersions are tabulated for each glass type in the data sheets. $\begin{matrix} \begin{matrix} {{PC},{t = {\left( {{nC} - {nt}} \right)/\left( {{nF} - {nC}} \right)}}} & {{Pg},{F = {\left( {{ng} - {nF}} \right)/\left( {{nF} - {nC}} \right)}}} \\ {{PC},{s = {\left( {{nC} - {ns}} \right)/\left( {{nF} - {nC}} \right)}}} & {{Pi},{g = {\left( {{ni} - {ng}} \right)/\left( {{nF} - {nC}} \right)}}} \\ \left. {{PF},{e = {{\left( {{nF} - {ne}} \right)/{nF}} - {nC}}}} \right) & \quad \end{matrix} & (4) \end{matrix}$

PC, s and Pg,F are plotted versus the Abbe-value nd in a diagram enclosed with the catalog. The position of the normal lines is determined based on value pairs of the glass types K7 and F2. $\begin{matrix} {{PC},{t = {0.5450 + {0.004743 \cdot {nd}}}}} & {{Pg},{F = {0.6438 - {0.001682 \cdot {nd}}}}} \\ {{PC},{s = {0.4029 + {0.002331 \cdot {nd}}}}} & {{Pi},{g = {1.7241 - {0.008382 \cdot {nd}}}}} \\ {{PF},{e = {0.4884 - {0.000526 \cdot {nd}}}}} & \quad \end{matrix}$

(See also Property of Optical Glass, Chapter 214+215, and pp. 27-33.)

The glasses according to the invention were produced as follows: the raw materials for the oxides, preferably free carbonates or nitrates, were pre-mixed, the fining agent was added, and the components were then mixed thoroughly. The glass batch was melted in a batch melting unit at melting temperatures of from about 1180° C. to 1220° C., then fined and homogenized well. The casting temperature was about 950° C.

Tables 1 and 2 show melt examples.

TABLE 1 Melt example for 100 kg of calculated glass Oxide % by weight Raw material Weight [kg] SiO₂ 22.0 SiO₂ 22.0 B₂O₃ 20.0 H₃BO₃ 35.7 Na₂O 5.0 Na₂CO₃ 8.6 CaO 0.5 CaCO₃ 0.9 BaO 20.0 BaCO₃ 23.3 ZnO 5.0 ZnO 5.0 TiO₂ 15.0 TiO₂ 15.0 ZrO₂ 1.0 ZrO₂ 1.0 Y₂O₃ 1.0 Y₂O₃ 1.0 La₂O₃ 0.5 La₂O₃ 0.5 Gd₂O₃ 1.0 Gd₂O₃ 1.0 Nb₂O₅ 9.0 Nb₂O₅ 9.0 Sb₂O₃ 0.2 Sb₂O₃ 0.2 Σ 100.2 123.2

The properties of the resultant glass are shown in Table 2, Example 3. Examples 1 and 7 show compositions close to the edges of the claimed composition range and accordingly represent, even among the examples, the extremes with respect to refractive index and Abbe number. However, their physical properties correspond to those of the glasses from the narrower preferred composition ranges.

TABLE 2 Glass compositions (in % by weight, based on oxide) and essential properties of the glasses 1 2 3 4 5 6 7 SiO₂ 11 16.5 22 17 22 25 25 B₂O₃ 10 10 20 16 18 10 20 Na₂O 2.5 2 5 4 4 7 8 K₂O — 0.5 — — 1 — — CaO 3 3 0.5 1.5 0.5 3 3 BaO 30 30 20 29 18 22 22 ZnO 12 12 5 9 7 12 5 TiO₂ 15 6 15 10 15 6 7 ZrO₂ 5 5 1 4 3 5 2 Y₂O₃ 1 1 1 0.5 1 1 1 La₂O₃ 0.5 8 0.5 1 0.5 1 1 Nb₂O₅ 10 6 9 8 9 8 6 Gd₂O₃ — 1 — — — — — Ta₂O₅ — — — — 1 — — Sb₂O₃ 0.2 0.2 0.2 0.2 0.2 0.2 0.2 n_(d) 1.8478 1.7634 1.6697 1.7449 1.7484 1.7103 1.6697 ν_(d) 28.82 37.55 41.21 34.89 30.59 38.11 41.22 P_(g, F) 0.6033 0.5794 0.6021 0.5893 0.6023 0.5786 0.5743 Δ P_(g, F) [10⁻⁴] 80 −12 105 40 99 −11 −1 ρ [g/cm³] 4.12 4.11 3.35 3.71 3.40 3.63 3.32 α_(20/300) [10⁻⁶/K.] 9.1 9.0 7.6 8.4 7.5 8.9 8.9 T_(g) [° C.] 568 574 551 556 557 547 551 UDL [° C.] 1130 1050 1125 n.m. n.m. 870 * *= no devitrification (measurement range 755-1200° C.) n.m. = not measured

The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. 

What is claimed is:
 1. An essentially lead-free or lead-free optical glass having a refractive index n_(d) of from 1.65 to 1.87 and an Abbe number ν_(d) of from 27 to 43, and comprising in % by weight, based on oxide: SiO₂ 10-25 B₂O₃ ≧10-25    Na₂O 2.5-10  K₂O 0-3 CaO 0.5-5   BaO 15-30 ZnO  5-15 TiO₂  6-15 ZrO₂ 0.5-8   Y₂O₃ 0.1-2   La₂O₃ 0.5-8   Nb₂O₅  6-12 with La₂O₃ + Nb₂O₅ ≦17 Ta₂O₅ 0-1 Gd₂O₃ 0-1

and optionally a fining agent.
 2. The glass according to claim 1, wherein the ZrO₂/TiO₂ weight ratio is from 0.06 to 0.85.
 3. The glass according to claim 2, wherein the glass comprises refractive index n_(d) of from 1.66 to 1.85 and an Abbe number ν_(d) of from 28 to 42, and in % by weight, based on oxide: SiO₂ 10-25 B₂O₃ ≧10-20    Na₂O 2.5-8   CaO 0.5-5   BaO 18-30 ZnO  5-15 TiO₂  6-15 ZrO₂ 1-5 Y₂O₃ 0.2-2   La₂O₃ 0.5-8   Nb₂O₅  6-10 with La₂O₃ + Nb₂O₅ ≦14 Ta₂O₅ 0-1 Gd₂O₃  0-1.


4. The glass according to claim 1 comprising a refractive index n_(d) of from 1.70 to 1.79 and an Abbe number ν_(d) of from 30 to 39, and in % by weight, based on oxide: SiO₂ 15-25 B₂O₃ ≧10-20    Na₂O 2.5-7   CaO 0.5-3   BaO 18-30 ZnO  5-12 TiO₂  6-15 ZrO₂ 1-5 Y₂O₃ 0.2-2   La₂O₃ 0.5-8   Nb₂O₅  6-10 with La₂O₃ + Nb₂O₅ ≦14.


5. The glass according to claim 1 comprising a refractive index n_(d) of from 1.73 to 1.77 and an Abbe number ν_(d) of from 33 to 37, and in % by weight, based on oxide: SiO₂ 15-20 B₂O₃ 14-29 Na₂O 3-6 CaO 0.5-2.5 BaO 25-30 ZnO  7-11 TiO₂  7-12 ZrO₂ 2.5-5   Y₂O₃ 0.2-0.5 La₂O₃ 0.5-2   Nb₂O₅   7-9.5 with La₂O₃ + Nb₂O₅ ≦11.


6. The glass according to claim 1, further comprising about 0.1 to about 0.5% by weight of Sb₂O₃.
 7. The glass according to claim 1, further comprising up to about 0.5% by weight of fluoride.
 8. The glass according to claim 1, wherein the glass is essentially free from arsenic oxide.
 9. In an optical component comprising a glass, the improvement wherein the essentially lead-free or lead-free glass is a glass of claim
 1. 10. An essentially lead-free or lead-free optical glass having a refractive index n_(d) of from 1.65 to 1.87 and an Abbe number ν_(d) of from 27 to 43, and comprising in % by weight, based on oxide: SiO₂ about 10-about 25 B₂O₃ ≧ about 10-about 25 Na₂O about 2.5-about 10 K₂O about 0-about 3 CaO about 0.5-about 5 BaO about 15-about 30 ZnO about 5-about 15 TiO₂ about 6-about 15 ZrO₂ about 0.5-about 8 Y₂O₃ about 0.1-about 2 La₂O₃ about 0.5-about 8 Nb₂O₅ about 6-about 12 with La₂O₃ + Nb₂O₅ ≦ about 17 Ta₂O₅ 0-about 1 Gd₂O₃ 0-about 1

and optionally a fining agent. 